CN100382337C - Method for preparing titanium dioxide nanocrystalline light scattering thin film electrode - Google Patents
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- CN100382337C CN100382337C CNB2005100115237A CN200510011523A CN100382337C CN 100382337 C CN100382337 C CN 100382337C CN B2005100115237 A CNB2005100115237 A CN B2005100115237A CN 200510011523 A CN200510011523 A CN 200510011523A CN 100382337 C CN100382337 C CN 100382337C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention belongs to the field of the manufacture technology of a dye-sensitized TiO2 nano-crystal light scattering film electrode and a photocatalysis electrode, particularly to a method for preparing a TiO2 nano-crystal light scattering film electrode by a TiO2 paste solution formed by mixing spherical pore forming agents and TiO2 granule colloid. The electrode comprises a conductive substrate and a nano-crystal light scattering film formed by the method that TiO2 slurry is generated on the substrate, and the nano-crystal light scattering film is provided with macroporous structures with hundreds of nanometers of air, which are randomly embedded and distributed in film material. The present invention has the advantages of high light scattering performance, simple preparation method and simple operation, and is especially suitable for the preparation of the commercial process of the TiO2 nano-crystal light scattering film electrode; the prepared TiO2 nano-crystal light scattering film electrode can be applied to the fields of a dye-sensitized solar cell, a photoelectrocatalysis electrode, etc.
Description
Technical field
The invention belongs to dye sensitization TiO
2The manufacturing technology field of nanocrystalline light scattering thin film electrode and photochemical catalyst electrode, particularly a kind of by spherical pore creating material and TiO
2The TiO that the granule colloid mixes
2Pulp solution prepares TiO
2The method of nanocrystalline light scattering thin film electrode.
Background technology
At dye sensitization TiO
2In the nano-crystal thin-film solar cell, dye sensitization TiO
2Nano-crystal thin-film is by TiO
2The crystalline phase of receiving connects and forms porous network shape structure, and the photosensitive molecular absorption luminous energy that is adsorbed on the nano-crystal thin-film surface is the prerequisite of DSSC opto-electronic conversion, and improving efficiency of light absorption is an important key that improves the cell photoelectric conversion efficiency.Present widely used Ru-polypyridine dyestuff has efficient absorption to 400～600nm visible light, but (600～900nm) extinction ability wretched insufficiency has limited the raising of photoelectric conversion efficiency at ruddiness and near infrared band.At design TiO
2Introduce the light scattering center during film microstructure, utilizing light scattering effect to increase light path is an important channel of improving efficiency of light absorption and then improving photoelectric conversion efficiency.
TiO
2The light scattering characteristic of nano-crystal thin-film is with to receive brilliant particle size relevant.Big particle diameter receive crystal grain the light scattering factor mean value than small particle diameter to receive crystal grain big.The TiO of extensive use now
2The preparation method of nanocrystalline light scattering thin film electrode receives crystal grain and 10～30nm TiO with the big particle diameter of 100～400nm
2The light scattering thin film electrode that the granule colloid mixes by a certain percentage.CoordinationChemistry Reviews for example, 2004, V.248.1381～1389 and J.Am.Chem.Soc, 2004, V.126.13590～13591 in the method for preparing light scattering thin film electrode of report.The advantage of this light scattering thin film electrode is that the preparation method is simple, and big particle diameter is received the size of crystal grain and regulated easily.Can be little but big particle diameter is received the crystal grain sub-surface, big particle diameter is received crystal grain and granule TiO in film
2Between compatibility bad, TiO
2Between the size particles and combine firmly inadequately between particle and the conductive substrates, can not form good electrical contact, thereby limit the stability of electron transport speed and electrode in the nano-crystal thin-film.
TiO
2The light scattering characteristic of nano-crystal thin-film is also relevant with change of refractive.Index contrast is big more in the film, and it is big more to obtain the Na crystal porous membrane light scattering property.The pore that retains in film can be the light scattering center also, makes light produce scattering, and light scattering property and aperture are closely related.Receive the molecular TiO of brilliant granule
2Film is transparent, not necessarily forms higher scattering coefficient though film has higher porosity, and this is because the 25nm spilehole is than the cause of visible wavelength much shorter in the film.Cycle by the adjusting refractive index changes the efficiency of light absorption that the photonic crystal of making can improve nano-crystal thin-film.The diffraction effect of utilizing the periodic micro structure of photonic crystal that light wave is had, when light was propagated in photonic crystal, diffraction effect had limited optical transmission, diffraction maximum occurred.J.Am.Chem.Soc for example, 2003, V.125.6306～6310 and Solar Energy Materials ﹠amp; Solar Cells, 2005, V.85.115～124 in the report the method for preparing the photon crystal film electrode.But the strict orderly periodic structure of photonic crystal has determined layer of photonic crystals to have strict band edge position on the one hand, it is narrow to make that layer of photonic crystals improves the wave band of efficiency of light absorption of nano-crystal thin-film, can not make efficiency of light absorption that general raising be arranged at red light district or the nearly red light district than broad; The synthetic of photonic crystal wasted time and energy very much at present on the other hand, greatly differ from each other with dye sensitization nano-crystal thin-film solar cell low price, preparation technology's characteristic of simple, and also since preparation technology's restriction, large-area TiO
2Photon crystal film is difficult to obtain, and this is unfavorable for that the absorption of a large amount of dye molecules can improve the luminous energy absorption efficiency of battery, has therefore influenced photonic crystal at dye sensitization TiO
2The application prospect of nano-crystal thin-film solar cell.
Goal of the invention
A purpose of the present invention is to overcome the deficiency of above-mentioned prior art, and a kind of preparation method of titanium dioxide nanocrystalline light scattering thin film electrode is provided.Adopt spherical pore creating material and TiO
2The method that the granule colloid mixes prepares TiO
2Slurry, and with TiO
2Slurry coating can make the TiO that has good stability after the heat treatment on conductive substrates
2Nanocrystalline light scattering thin film electrode.This kind nanocrystalline light scattering film has inlays the hundreds of nanometer air macroporous structure that is distributed in the thin-film material at random as scattering center.
Another object of the present invention is to provide preparation dye sensitization TiO
2The method of nanocrystalline light scattering thin film electrode.
In the titanium dioxide nanocrystalline light scattering film of the inventive method preparation, compact arranged small particle diameter titanium dioxide nanocrystalline particle surrounds the spherical air macroporous structure of hundreds of nanometer.Thisly inlay the air macroporous structure that is distributed in the nano-crystal thin-film material at random and the refractive index of titanic oxide material itself is very different.The refractive index of titanium dioxide nanocrystalline is higher, and air macropore refractive index is low, produces light scattering effect.After being assembled into solar cell, the air macropore is filled by electrolyte medium, the refractive index of the electrolyte medium also refractive index than titanic oxide material itself is low, the light scattering property size of nano-crystal thin-film is relevant with the refractive index size of electrolyte medium, the crystalline substance of receiving differs greatly with the electrolyte medium refractive index, and its light scattering property is also big.
This light scattering thin film electrode not only has the luminous energy absorption efficiency that light scattering effect can improve battery, and the existence of the macroporous structure in the nano-crystal thin-film material also helps the improvement of the electrolyte ion diffusion property in the film, and then the photoelectric conversion efficiency of raising battery, especially the solid-state TiO big for electrolyte viscosity, that mass transfer velocity is slow
2Nano-crystal thin-film solar cell has great importance.
The TiO of the present invention's preparation
2Nanocrystalline light scattering thin film electrode light scattering property height, and have preparation method's characteristics simple, easy and simple to handle, be easy to dye sensitization TiO
2The suitability for industrialized production of nanocrystalline light scattering thin film electrode is easy to obtain high-quality large area film, thereby has expanded dye sensitization TiO greatly
2The application prospect of nano-crystal thin-film solar cell.
Titanium dioxide nanocrystalline light scattering thin film electrode of the present invention comprises two kinds of single layer structure and sandwich constructions.
The preparation method of the titanium dioxide nanocrystalline light scattering thin film electrode of single layer structure may further comprise the steps:
(1) presses document J.Phys.Chem.B, 2000, V.104.4130～4133, J.Phys.Chem.B, 1997, V.101.55～57 and J.Am.Chem.Soc, 1993, V.115.6382～6390 reported method prepares titanium dioxide granule colloid in, and the solid content of titanium dioxide is 12～17% in colloid;
(2) according to the weight ratio of the solid titanium dioxide in the titanium dioxide granule colloid of spherical pore creating material and step (1) be 1: 1～1: 20 ratio, be preferably 1: 20 ratio, with spherical pore creating material with make titania slurry after the titanium dioxide granule colloid of step (1) mixes;
(3) titania slurry that step (2) is made evenly applies (as coating process or other coating method) and make the titanium dioxide membrane electrode provided semi-finished product on the conductive substrates that cleans up;
(4) the titanium dioxide membrane electrode provided semi-finished product that step (3) is prepared are heat-treated under 430～470 ℃, obtain the titanium dioxide nanocrystalline light scattering thin film electrode of single layer structure.
The titanium dioxide nanocrystalline light scattering thin film electrode of above-mentioned single layer structure, the rear orientation light of close conductive substrates is unfavorable for that incident light enters film, for overcoming this shortcoming, the titanium dioxide nanocrystalline light scattering thin film electrode that can design sandwich construction improves.Do not add pore creating material with ground floor that conductive substrates directly contacts in design during sandwich construction, near conductive substrates, TiO
2The particle diameter of crystal grain received is little, and the back scattering light loss is little, helps incident light and enters in the film.Directly contact densely between conductive substrates and the ground floor, can also reduce that transmission medium contacts with conductive substrates and the electron recombination probability that causes.Each layer of other that cover on ground floor can increase the ratio of pore creating material or the size of pore creating material gradually, and the air macroporous structure in these layers can increase light path, improves efficiency of light absorption.When improving light scattering property, the air macroporous structure can also improve the ions diffusion characteristic in the solution, helps electrolytical infiltration, reduces the loss of voltage that concentration polarization that mass transfer causes causes, and further improves photoelectric conversion efficiency.
The preparation method of the titanium dioxide nanocrystalline light scattering thin film electrode of sandwich construction may further comprise the steps:
(1) presses document J.Phys.Chem.B, 2000, V.104.4130～4133, J.Phys.Chem.B, 1997, V.101.55～57 and J.Am.Chem.Soc, 1993, V.115.6382～6390 reported method prepares titanium dioxide granule colloid A in, and the solid content of titanium dioxide is 12～17% in colloid;
(2) the titanium dioxide granule colloid A with step (1) evenly applies (as coating process or other coating method) on the conductive substrates that cleans up, and makes the elementary semi-finished product of titanium dioxide membrane electrode provided;
(3) the elementary semi-finished product of titanium dioxide membrane electrode provided that step (2) is prepared are heat-treated under 430～470 ℃;
(4) according to the weight ratio of the solid titanium dioxide among the titanium dioxide granule colloid A of spherical pore creating material and step (1) be 1: 1～1: 20 ratio, be preferably 1: 20 ratio, with spherical pore creating material with make titania slurry B after the titanium dioxide granule colloid A of step (1) mixes;
(5) the titania slurry B of step (4) evenly is coated in above the elementary semi-finished product of titanium dioxide membrane electrode provided that step (3) prepares, obtains the titanium dioxide membrane electrode provided semi-finished product;
(6) the titanium dioxide membrane electrode provided semi-finished product that step (5) is prepared are heat-treated under 430～470 ℃, make the titanium dioxide nanocrystalline light scattering thin film electrode of sandwich construction.
In the process of repeating step (4)～(6), can increase the ratio or the size of pore creating material, make the titanium dioxide nanocrystalline light scattering thin film electrode of sandwich construction.
Light-scattering film in the described titanium dioxide nanocrystalline light scattering thin film electrode is that spherical air macropore and the titanium dioxide granule of 100～1000nm formed by the diameter of random distribution.Diameter and the quantity that has been determined macropore in the described light-scattering film by the titania slurry of the ratio of different pore creating materials or size composition is used in preparation during titanium dioxide nanocrystalline light scattering thin film electrode.
The particle diameter of described titanium dioxide granule colloid small particles is 6～50nm.
Described conductive substrates is a transparent conducting glass.
Described spherical pore creating material is water-insoluble macromolecular material.Described water-insoluble macromolecular material is selected from acrylic sphere, polyethylene ball or polystyrene spheres, is preferably polystyrene spheres.
The particle diameter of the spherical pore creating material among the present invention is chosen as 100～1000nm, is preferably 200nm.
Titanium dioxide membrane electrode provided among the present invention need be heat-treated.Heat treatment has two effects, and one of effect is to remove spherical pore creating material, stays corresponding spherical air macroporous structure on its position, and two of effect is to make TiO
2Between the granule colloid and TiO
2Combine firmly between granule colloid and the conductive substrates.Heat treatment temperature is 430～470 ℃ among the present invention.
Among the preparation method of titanium dioxide nanocrystalline light scattering thin film electrode of the present invention, described titanium dioxide granule colloid can adopt any known preparation method acquisition in this area, J.Phys.Chem.B for example, 2000, V.104.4130～4133, J.Phys.Chem.B, 1997, V.101.55～57 and J.Am.Chem.Soc, 1993, V.115.6382～6390 reported method in, these documents are incorporated herein by reference with it in full at this.
The titanium dioxide nanocrystalline light scattering thin film electrode of the present invention's preparation is specially adapted to the TiO in the dye sensitization nano-crystal thin-film solar cell
2Work electrode.
The present invention will be illustrated by the following examples.But, be to be understood that the present invention is not limited to particular example as described herein and embodiment.The purpose that comprises these particular example and embodiment here is to help those of skill in the art to put into practice the present invention.Any those of skill in the art are easy to be further improved without departing from the spirit and scope of the present invention and perfect, therefore the present invention only is subjected to the restriction of the content and the scope of claim of the present invention, and its intention contains all and is included in interior alternative or the equivalent of spirit and scope of the invention that appendix claim limits.
The subordinate list explanation:
Table 1 is to use titanium dioxide nanocrystalline light scattering thin film electrode that the present invention prepares and the platinum photoelectric properties to the DSSC of electrode assembling.
TiO
2The coating method of slurry: the both sides of the conductive substrates that cleans up are fixed with adhesive tape, dipped in the TiO that takes a morsel with glass bar
2Slurry also is coated onto it on conductive substrates equably, preparation TiO
2Membrane electrode.Thickness with adhesive tape when filming is controlled TiO
2The thickness of film.
The preparation method of the titanium dioxide nanocrystalline light scattering thin film electrode after the dye sensitization: the titanium dioxide nanocrystalline light scattering thin film electrode that the present invention is made heated 0.5～1 hour in temperature is 80～100 ℃ baking oven.Subsequently titanium dioxide nanocrystalline light scattering thin film electrode is immersed 5 * 10
-4M 4,4 '-dicarboxylic acids bipyridyl ruthenium is (along two thiocyanates-two (2,2 '-bipyridine-4,4 '-dicarboxylic acids) close ruthenium (II)) ethanolic solution in take out after 8～16 hours, with drying the titanium dioxide nanocrystalline light scattering thin film electrode that can make after the dye sensitization after the absolute ethyl alcohol flushing.
Method of measurement:
With dyestuff 4, the TiO for preparing among 4 '-dicarboxylic acids bipyridyl ruthenium (along closing ruthenium (II) in two thiocyanates-two (2,2 '-bipyridine-4,4 '-dicarboxylic acids)) sensitization the present invention
2Nanocrystalline light scattering thin film electrode uses the platinized platinum conduct to electrode as work electrode.With containing 0.5M LiI, 0.05M I
2With the trimethoxy propionitrile solution of 0.5M four tertiary butyl pyridines as electrolyte, be assembled into DSSC and carry out performance measurement.
(Model 273, EG﹠amp for potentiostat/galvanostat that the photoelectric properties of battery are computerizedd control; G) at room temperature measure.Light source uses 250W tungsten halogen lamp, incident intensity 60mW/cm
2, illuminating area 0.2cm
2
Embodiment
Embodiment 1
Prepare titanium dioxide granule colloid by reported method in the document, the solid content of titanium dioxide is 12% in colloid; Weight ratio according to polystyrene spheres and titanium dioxide is 1: 20, takes by weighing the TiO of 100nm particle diameter polystyrene spheres and 20nm particle diameter
2The granule colloid is put in to grind after 4 hours in the mortar and makes TiO
2Slurry;
The SnO of fluorine is mixed in use
2Electro-conductive glass (FTO) (Heilungkiang Haake new forms of energy Co., Ltd, square resistance 30 Ω cm
-2) as conductive substrates.The titania slurry that makes evenly is coated in makes the titanium dioxide membrane electrode provided semi-finished product on the conductive substrates that cleans up; The titanium dioxide membrane electrode provided semi-finished product that prepare were heat-treated under 450 ℃ 30 minutes, obtain TiO of the present invention
2Nanocrystalline light scattering thin film electrode.
Embodiment 2
Except that the polystyrene spheres particle diameter being changed into 200nm, obtain TiO of the present invention as the method among the embodiment 1
2Nanocrystalline light scattering thin film electrode.
Embodiment 3
Remove and change the polystyrene spheres particle diameter into 450nm, TiO
2Granule particle diameter in the granule colloid changes into beyond the 40nm, obtains TiO of the present invention as the method among the embodiment 1
2Nanocrystalline light scattering thin film electrode.
Embodiment 4
Except that polystyrene spheres being changed into the acrylic sphere of particle diameter 1000nm, obtain TiO of the present invention as the method among the embodiment 1
2Nanocrystalline light scattering thin film electrode.
Embodiment 5
Except that weight ratio was changed into 1: 10, obtain TiO of the present invention as the method among the embodiment 2
2Nanocrystalline light scattering thin film electrode.
Embodiment 6
Except that weight ratio was changed into 1: 5, obtain TiO of the present invention as the method among the embodiment 2
2Nanocrystalline light scattering thin film electrode.
Embodiment 7
Except that weight ratio was changed into 1: 1, obtain TiO of the present invention as the method among the embodiment 2
2Nanocrystalline light scattering thin film electrode.
Embodiment 8
Prepare titanium dioxide granule colloid A by reported method in the document, the solid content of titanium dioxide is 12% in colloid; Weight ratio according to polystyrene spheres and titanium dioxide is 1: 20, takes by weighing the TiO of 100nm particle diameter polystyrene spheres and 20nm particle diameter
2The granule colloid is put in to grind after 4 hours in the mortar and makes TiO
2Slurry B.
The SnO of fluorine is mixed in use
2Electro-conductive glass (FTO) (Heilungkiang Haake new forms of energy Co., Ltd, square resistance 30 Ω cm
-2) as conductive substrates, the both sides of conductive substrates are fixed with adhesive tape, dip in glass bar and get titanium dioxide granule colloid A and being coated onto equably on the conductive substrates, make the elementary semi-finished product of titanium dioxide membrane electrode provided; After treating that it parches, be heat treatment 10 minutes and in air, naturally cool to room temperature under 450 ℃ the condition in temperature, then the elementary half-finished both sides of titanium dioxide membrane electrode provided fixed with adhesive tape, dip in glass bar and get TiO
2Slurry B also is coated onto on the elementary semi-finished product of titanium dioxide membrane electrode provided equably, obtains the titanium dioxide membrane electrode provided semi-finished product; With titanium dioxide membrane electrode provided semi-finished product natural airing in air, with its 450 ℃ of heat treatment 30 minutes in Muffle furnace, can make TiO of the present invention then
2Nanocrystalline light scattering thin film electrode.
Embodiment 9
Remove TiO
2The polystyrene spheres particle diameter changes into beyond the 200nm among the slurry B, can obtain TiO of the present invention as same procedure among the embodiment 8
2Nanocrystalline light scattering thin film electrode.
Embodiment 10
Remove TiO
2The polystyrene spheres particle diameter changes 450nm among the slurry B, TiO
2Granule particle diameter in the granule colloid changes into beyond the 40nm, can obtain TiO of the present invention as same procedure among the embodiment 8
2Nanocrystalline light scattering thin film electrode.
Embodiment 11
Remove TiO
2The polystyrene spheres particle diameter changes into beyond the 1000nm among the slurry B, can obtain TiO of the present invention as same procedure among the embodiment 8
2Nanocrystalline light scattering thin film electrode.
Embodiment 12
Remove and use titanium dioxide granule colloid A also to be coated onto equably on the elementary semi-finished product of titanium dioxide membrane electrode provided, obtain beyond the titanium dioxide membrane electrode provided semi-finished product, obtain not having the TiO of air macroporous structure as same procedure among the embodiment 8
2The nano-crystal thin-film electrode.
Table 1
Claims (6)
1. the preparation method of a titanium dioxide nanocrystalline light scattering thin film electrode, it is characterized in that: this method may further comprise the steps:
(1) preparation titanium dioxide granule colloid, the solid content of titanium dioxide is 12～17% in colloid;
(2) according to the weight ratio of the solid titanium dioxide in the titanium dioxide granule colloid of spherical pore creating material and step (1) be 1: 1～1: 20 ratio, with spherical pore creating material with make titania slurry after the titanium dioxide granule colloid of step (1) mixes;
(3) titania slurry that step (2) is made evenly is coated in and makes the titanium dioxide membrane electrode provided semi-finished product on the conductive substrates that cleans up;
(4) the titanium dioxide membrane electrode provided semi-finished product that step (3) is prepared are heat-treated under 430～470 ℃, obtain the titanium dioxide nanocrystalline light scattering thin film electrode of single layer structure;
Described spherical pore creating material is selected from acrylic sphere, polyethylene ball or polystyrene spheres.
2. method according to claim 1 is characterized in that: the particle diameter of described titanium dioxide granule colloid small particles is 6～50nm.
3. method according to claim 1 is characterized in that: the particle diameter of described spherical pore creating material is 100～1000nm.
4. the preparation method of a titanium dioxide nanocrystalline light scattering thin film electrode, it is characterized in that: this method may further comprise the steps:
(1) preparation titanium dioxide granule colloid A, the solid content of titanium dioxide is 12～17% in colloid;
(2) the colloidal tio 2 A with step (1) evenly is coated on the conductive substrates that cleans up, and makes the elementary semi-finished product of titanium dioxide membrane electrode provided;
(3) the elementary semi-finished product of titanium dioxide membrane electrode provided that step (2) is prepared are heat-treated under 430～470 ℃;
(4) weight ratio according to the solid titanium dioxide among the titanium dioxide granule colloid A of spherical pore creating material and step (1) is the ratio of 1:1～1:20, with spherical pore creating material with make titania slurry B after the titanium dioxide granule colloid A of step (1) mixes;
(5) the titania slurry B of step (4) evenly is coated in above the elementary semi-finished product of titanium dioxide membrane electrode provided that step (3) prepares, obtains the titanium dioxide membrane electrode provided semi-finished product;
(6) step (5) is prepared the titanium dioxide membrane electrode provided semi-finished product and under 430～470 ℃, heat-treat, make the titanium dioxide nanocrystalline light scattering thin film electrode of sandwich construction;
Described spherical pore creating material is selected from acrylic sphere, polyethylene ball or polystyrene spheres.
5. method according to claim 4 is characterized in that: the particle diameter of described titanium dioxide granule colloid small particles is 6～50nm.
6. method according to claim 4 is characterized in that: the particle diameter of described spherical pore creating material is 100～1000nm.
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| CN1909261B (en) * | 2006-08-28 | 2011-10-26 | 清华大学 | Titanium dioxide crystallized light absorption enhancement thin film electrode and its preparation method |
| CN102915845A (en) * | 2012-10-17 | 2013-02-06 | 天津大学 | Semiconductor film with gradually increased hole diameters of different layers and preparation method thereof |
| CN103232172B (en) * | 2013-04-16 | 2016-01-20 | 同济大学 | Big area prepares the method for nano titania hollow ball order thin film |
| EP3012022A4 (en) * | 2013-06-21 | 2017-03-08 | Toto Ltd. | Visible light responsive photocatalyst material |
| CN108538603A (en) * | 2018-03-29 | 2018-09-14 | 中国石油大学(华东) | A kind of open structure titanium deoxid film |
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| WO2003008079A2 (en) * | 2001-07-18 | 2003-01-30 | University Of Massachusetts | Metal oxide films |
| CN1411077A (en) * | 2001-09-26 | 2003-04-16 | 北京科技大学 | Nano titanium dioxide film and its manufacturing method |
| CN1444292A (en) * | 2003-01-09 | 2003-09-24 | 中国科学院等离子体物理研究所 | Novel nano porous film and preparation method thereof |
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